Green dye and process of making same.



PAUL JULIUS, OF LUD'WTGSHAFEN-GN-THE-RI-IINE, GERMANY.

ljATENT OFFICE.

ASSIGNOR TO BADISC-HE ANIL IN 1k SODA FABRIK, Ol LU'DW'IGSHAFEN-OX-THE-RHIN E, GERMANY, A CORPORA- TION OF GERMANY.

Application filed February 21, 1907.

To all whom it may concern:

Be it'known that I, PAUL JULIUS, doctor of philosophy and chemist, subject of the Emperor of Austria, residing; at Ludwigs- 5 halen-on-thelihine, Germany, have invented new and useful Improvements in Green Dyes and Processes of Making" the Same, of which the following is a specifica' tion.

My invention relates to the production of green coloring matters of the triphenylmethane series by condensing a dinitrodi- )henylamin disullonie acid compound as hereinafter defined with an allzylated di 1 5 lnatters are obtained in the form of their leuco compounds, these leuco compounds, on 'oxidation, bein; converted into the coloring matters proper which dye wool green shades possessing excellent properties, being fast against the action of alkalies, Washing, and potting.

The dinitrodi )henylamin disulfonic acid compounds which can he used according to my invention include those obtainable by reacting on inetanilio aeidwith' either 01' the two isomeric (linitrochlorbenzene sulfonic acids f and further instead of the above mentioned dinitrochlorbenzene sulfonic acids, derivatives thereof can be employed, and also in stead of metanilio acid, derivatives of metanilic acid, in which the para position to the amidogroup is only occupied by hyrdogen,-

s from these solutions dye wool yieldil'ig full green shades. Their aqueous solutions turn yellow upon the additionof mineral acid, and the coloring matters thei'nsclves yield yellow solutions in concentrated sulfuric acid. They possess, lLO\V(-.\'(X., the following characteristics which differentiate then-1 from the hitherto known coloring uni-tiers, via. their aqueous solutn'ms are green and iurn Ylol0tblue upon the addition of caustic soda in [h cold, and further tln-y contain intro groups Specification of Letters Patent.

7 the presence of which can be proved in dil' amidobenzhydrol, whereupon the coloring GREEN DYE AND IROCESS OF MAKING SAME.

Patented May 5, 1908.

Serial No. 358,537.

fcrent ways, for instance upon reduction with zinc and acetic acid and upon subsequent oxidation they do not yield back the original coloring matters.

The coloring matter which I wish to be understood as claiming specifically is that obtainable by condcsing .2.6 :linitrodiphenyla1nin4.3-d.isulfonic acid. with tetramethyldiamidobenzhydrol and in particular in the form of its sodium salt it possesses a composition corresponding to the formula.

The following Example 1 will hel to show how the dinitrodiphenylaniin disullonic acid compounds which are used in my invention can be prepared, and Example 2 shows how my invention can be carried into practical effect, but my invention is not confined to this example. The parts are by weight and the temperatures are given in degrees centigrade.

Example 1-. Dissolve two hundred and eighty-two and a half (282.5) parts of 2.6- dinitrochlorbenzene- L-sullonie acid in seven (7) times its Weight of water, and allow a concentrated aqueous solution of one hundred and seventy-three (173) arts of metanilie acid and four hundred anr ten (410) parts of crystallized sodium acetate to flow into the hot solution. This addition should extend over a period of aboutthirty (30) minutes, and the solution should be stirred during the addition. Then boil for about thirty (30) minutes and salt out the dinitrodiphonyl' ainin disulfonie acid formed, by means of potassium chlorid. This new compound can be recrystallized and obtained in the form of line golden needles which are easily soluble in water. In this example the dinitrochlorbenzene sullonic acid can be replaced by it's a-l'orcx'nontioncd isomer, and also instead of metanilic acid, a derivative thereof, such for illstztlltv as .lchlor-2 -amidobonZene-lsul tonic acid and orthotoluidin-parasulhmic 1 acid, can be l-mployed. t

Example 2. Mix well togetherforty-nine and a half (49.5) parts of the dipotassiurn salt of 2.6-dinitrodiphenylamin-4.I3-disul fonic acid and-twenty-seven (27) parts of tetramethyldiamidobenzhydrol, and 'intro duce the mixture, at ordinary temperature,

during a period of thirty (30) minutes, and while 'stirrin well, into two hundred '(200) parts of sul ric acid monohydrate, where upon the temperature rises to abbut fifty (50) degrees. Stir for one (1) hour, pour onto ice, and filter off the 'yellow'crystalline leuco compound which separates out, and press, and dry. This leuco-compound consists of an orange-yellow powder which is in' soluble in cold water, but easily soluble in dilute sodium carbonate solution and in caustic alkalies. In order'to convert it into coloring matter, dissolve thirty-three and three-fifths (33.6) parts-thereof and six (6) arts of sodium carbonate in fifteen hundred (1500) arts of water, and cool the solution to about teen (15) degrees, and add, "while stirring well, first four and three-fifths (4.6) parts of manganese dioxid in the form of a paste, and then sixty-five (65) parts of twenty-five (25) per cent. sulfuric acid. Stir for from three (3) to four (4) hours, boil, and filter the solution, then preci itate the coloring matter from the solution y' means of common salt, filter it off, and press, and d1- It dissolves in water yielding a green so ution, and dyes wool full green shades. Its aqueous solution, on the addition of mineral acid, assumes a yellow color, and the coloring matter also dissolves in concen- Correction in Letters Patent No; 886,815.

trated sulfuric acid yielding a yellow solution.

In a similar manner, coloring matters can be obtained by making use of other alkylated diamidobenzhydrols andalso of other dinitrothe application of Paul J ulius, improvement in Green Dyes and so rta 2 and that he said Letters Patent should should read I diphenylamindisulfonic acids. Further, instead of manganese dioxid, other oxidizing agents, for instance bichrornate, can be used,

Now what I claim. is:

1. The process of producing coloring matter of the triphenylmethane series by condensing a' hereinbefore defined dinitro-diphenylamin-disulfonic acid compound with an alkylated diamidobenzhydrol and oxidizing the resulting leuco compound.

2. The process of producing coloringmat- "ter of the triphenylmethane series by condensing 2.6(linitrodiphenylamin-4.3disulfonic acid with tetramthyldiamidobenzhydrol and oxidizing the resulting leuco compound. I 3. As new articles of manufacture triphenylmethane coloring matters containing nitro groups, which dye wool fromv an acid bath full green shades and whose aqueous solutions are green and turn violet-blue upon the addition of caustic alkali in the cold.

4. As a new article of manufacture the tri- 'phenylmethane coloringmatter which dyes wool from an acid bathiull green shades and whose aqueous solution is green and turns violet-blue upon the addition of caustic alkali in the cold and which in the form of its sodium salt possesses a composition corresponding to the formula PAUL JULIUS.

, Witnesses ERNEST REHRHARDT,

H. W. HARRIS.

l It is hereby certified that in Letters Patent No. 885,815, granted May 5,1908, upon of Ludwigshafen-on-the-Rhine, Germany, for an Processes of Making Same, an error occurs in the printed specification requiring correction, as follows Ihlines' 67- 75, page 1, the

be read with this correction therein that the same may'conform to the record of the case in the Patent Oflice.

Signed and sealed this, 30th (1a; of June, A. .D., 1908.

C. C. BILLINGS, I Acting Commissioner of Patents,

Example 2. Mix well togetherforty-nine and a half (49.5) parts of the dipotassiurn salt of 2.6-dinitrodiphenylamin-4.I3-disul fonic acid and-twenty-seven (27) parts of tetramethyldiamidobenzhydrol, and 'intro duce the mixture, at ordinary temperature,

during a period of thirty (30) minutes, and while 'stirrin well, into two hundred '(200) parts of sul ric acid monohydrate, where upon the temperature rises to abbut fifty (50) degrees. Stir for one (1) hour, pour onto ice, and filter off the 'yellow'crystalline leuco compound which separates out, and press, and dry. This leuco-compound consists of an orange-yellow powder which is in' soluble in cold water, but easily soluble in dilute sodium carbonate solution and in caustic alkalies. In order'to convert it into coloring matter, dissolve thirty-three and three-fifths (33.6) parts-thereof and six (6) arts of sodium carbonate in fifteen hundred (1500) arts of water, and cool the solution to about teen (15) degrees, and add, "while stirring well, first four and three-fifths (4.6) parts of manganese dioxid in the form of a paste, and then sixty-five (65) parts of twenty-five (25) per cent. sulfuric acid. Stir for from three (3) to four (4) hours, boil, and filter the solution, then preci itate the coloring matter from the solution y' means of common salt, filter it off, and press, and d1- It dissolves in water yielding a green so ution, and dyes wool full green shades. Its aqueous solution, on the addition of mineral acid, assumes a yellow color, and the coloring matter also dissolves in concen- Correction in Letters Patent No; 886,815.

trated sulfuric acid yielding a yellow solution.

In a similar manner, coloring matters can be obtained by making use of other alkylated diamidobenzhydrols andalso of other dinitrothe application of Paul J ulius, improvement in Green Dyes and so rta 2 and that he said Letters Patent should should read I diphenylamindisulfonic acids. Further, instead of manganese dioxid, other oxidizing agents, for instance bichrornate, can be used,

Now what I claim. is:

1. The process of producing coloring matter of the triphenylmethane series by condensing a' hereinbefore defined dinitro-diphenylamin-disulfonic acid compound with an alkylated diamidobenzhydrol and oxidizing the resulting leuco compound.

2. The process of producing coloringmat- "ter of the triphenylmethane series by condensing 2.6(linitrodiphenylamin-4.3disulfonic acid with tetramthyldiamidobenzhydrol and oxidizing the resulting leuco compound. I 3. As new articles of manufacture triphenylmethane coloring matters containing nitro groups, which dye wool fromv an acid bath full green shades and whose aqueous solutions are green and turn violet-blue upon the addition of caustic alkali in the cold.

4. As a new article of manufacture the tri- 'phenylmethane coloringmatter which dyes wool from an acid bathiull green shades and whose aqueous solution is green and turns violet-blue upon the addition of caustic alkali in the cold and which in the form of its sodium salt possesses a composition corresponding to the formula PAUL JULIUS.

, Witnesses ERNEST REHRHARDT,

H. W. HARRIS.

l It is hereby certified that in Letters Patent No. 885,815, granted May 5,1908, upon of Ludwigshafen-on-the-Rhine, Germany, for an Processes of Making Same, an error occurs in the printed specification requiring correction, as follows Ihlines' 67- 75, page 1, the

be read with this correction therein that the same may'conform to the record of the case in the Patent Oflice.

Signed and sealed this, 30th (1a; of June, A. .D., 1908.

C. C. BILLINGS, I Acting Commissioner of Patents,

It is hereby certified that in Letters Patent No. 8863315, granted May 5, 1908, upon the application of Paul Julius, of Ludwigshafen-on-thc-Ellino, Germany, for an improvement in Green Dyes and Processes of Mgbking Same," an error occurs in the printed specification requiring correction, as follows: In lines fi7-75, page 1, the formula.

and thatithe said Letters Patent should be read with this correction therein that the same may conform to the record of the case in the Patent Office.

Signed and sealed this 30th day of June, A. D., 1908.

[mm] c. o. BILLINGS,

Acting Commissioner of Patents. 

